Plastic compositions

ABSTRACT

Plastic compositions containing a three component system consisting of (1) poly(phenylene oxide) polymer, (2) certain bisphenoxy compounds having the formula: ##STR1## WHEREIN Z is bromine, m and m&#39;  are each integers having a value of 1-5 with the proviso that the total bromine atom content is from 6-10, and &#34;T&#34; is a straight or branched chain carbon group having 1-4 carbon atoms, and (3) an enhancing agent hereinafter defined.

RELATED PATENT APPLICATIONS

This application is a continuation-in-part of a co-pending application, Ser. No. 499,727, filed Aug. 22, 1974, now U.S. Pat. No. 4,016,138 and which in turn is a continuation of co-pending application, Ser. No. 330,823, filed Feb. 8, 1973, now abandoned. The entire specification in each of these cases, Ser. Nos. 330,823 and 499,727, are to be considered as incorporated herein by reference.

PRIOR ART

The prior art considered in conjunction with the preparation of this application is as follows: U.S. Pat. No. 1,979,145; U.S. Pat. No. 2,130,990; U.S. Pat. No. 2,186,367; U.S. Pat. No. 2,263,444; U.S. Pat. No. 2,239,033; U.S. Pat. No. 2,488,499; U.S. Pat. No. 2,738,351; U.S. Pat. No. 2,797,246; U.S. Pat. No. 2,930,815; U.S. Pat. No. 3,384,819; U.S. Pat. No. 3,403,036; U.S. Pat. No. 3,549,591; U.S. Pat. No. 3,560,441; U.S. Pat. No. 3,649;591; U.S. Pat. No. ,658,634; U.S. Pat. No. 3,666,692; U.S. Pat. No. 3,686,320; U.S. Pat. No. 3,697,456; U.S. Pat. NO. 3,717,609; U.S. Pat. No. 3,763,243; U.S. Pat. No. 3,787,506; German Pat. No. 891,549; German Pat. No. 1,139,636; German Pat. No. 2,054,522; Japanese Patent No. (72) 14,500 (and as cited in Volume 77, Chemical Abstracts, column 153737k, 1972); Chemical Abstracts, Volume 13, column 448⁵ ; Chemical Abstracts, Volume 31, column 7045⁹ ; Chemical Abstracts, Volume 52 (1958), column 4543-4544; Journal of the Chemical Society, pages 2972-2976 (1963); Journal of the American Chemical Society, Volume 57 (1935), pages 572-574 and Volume 76 (1954), page 2993; Journal of the Science of Food and Agriculture, Volume 20 (1969), pages 748-754; Philippine Journal of Science, Volume 34 (1927), page 159; and Japanese Patent publication 033,456 of 1974. All of these publications are to be considered as incorporated herein by reference.

BACKGROUND OF THE INVENTION

The present invention relates to plastic compositions containing a poly (phenylene oxide) polymer (herein sometimes referred to as PPO). More specifically, the present invention covers plastic compositions containing a three component system which consists of PPO, certain bis-phenoxy compounds (hereinafter defined) as flame retardants for said plastic compositions, and an exhancing agent (hereinafter defined) for said flame retardants.

PPO plastics and utility thereof are known in the art as exemplified by Encyclopedia of Polymer Science and Technology, Volume 10, pages 92-111, John Wiley & Sons, Inc., New York, 1969, and which publication is in toto incorporated herein by reference.

The need for flame retarding PPO plastics has also been recognized in the art as exemplified by Encyclopedia of Polymer Science and Technology, ibid, pages 100 and 103, and by U.S. Pat. No. 3,403,036.

The prior art has specifically recognized the problems of finding suitable flame retardants for PPO polymers in view of the fact that polymer systems differ substantially in both flammability characteristics and physical properties and there is no predictability whatsoever from one system to another. Thus in the Norris et al paper entitled "Toxicological and Environmental Factors Involved in the Selection of Decabromodiphenyl Oxide as a Fire Retardant Chemical", Applied Polymer Symposium No. 22, 195-219 (1973), the authors state: "A growing recognition of the huge annual toll taken by fire is resulting in more stringent flammability requirements for synthetic polymers in a variety of applications. Because of economic constraints and the need to produce flame resistant polymers without total replacement of existing manufacturing processes, increased flame resistance is generally achieved by incorporation of a fire retardant chemical in the finished product. This chemical is usually based on bromine, chlorine, phosphorus, or nitrogen and may either be chemically reacted or physically blended into the product. Since polymer systems differ markedly in both flammability characteristics and physical properties, selection of a suitable flame retardant depends on a variety of factors that severely limits the number of acceptable materials.

"A general class of synthetic polymers that require flame retardancy because of their use in electrical and high temperature applications, but pose severe problems in selecting a suitable flame retardant are the high performance thermoplastic resins such as thermoplastic polyesters, polyphenylene oxides, and acrylonitrile-butadiene-styrene (ABS) terpolymers. Some of the most important criteria for an acceptable flame retardant in these applications are:

1. It must be as effective as possible to minimize both cost and effect on polymer properties. Use levels may range up to 15% by weight.

2. It must have sufficient stability to withstand conditions encountered during polymer processing and use. Processing conditions (blending, extrusion, and molding) often involve temperatures exceeding 300° C. The flame retardant must tolerate these conditions without degradation or volatilization. Also, attention must be given to hydrolytic stability and oxidative degradation, particularly under extended service at high temperatures.

3. It must be compatible with the base polymer and exert minimal adverse effect on those properties that give the polymer its value. Some of these critical properties are tensile strength, impact strength, heat deflection temperature, shear strength, and flexural modulus.

4. Finally, the flame retardant must not interfere with attainment of desired product esthetics and form.

"Because of the stringent thermal stability requirements, only a very few compounds have been identified which can meet the necessary performance and economic criteria."

The resultant disadvantages in the utilization of various prior art materials as flame retardants, in general, for plastic compositions include, without limitation, factors such as thermal migration, heat instability, light instability, non-biodegradable, toxicity, discoloration, the large amounts employed in order to be effective, and the unpredictable end results obtained when using the same material in different plastics (note, for example, in Modern Plastics Encyclopedia, ibid, page 650, wherein octabromobiphenyl is suitable for use in polyolefins as a flame retardant therefor, but is not shown for use (or functionally equivalent) as such for the other 27 compositions listed such as ABS; polycarbonates, polystyrene, acrylics and polyurethanes). Thus, it can be seen that the field of flame retardancy is highly sophisticated and consequently requires substantial research effort to achieve a particular desired end result.

In conjunction with the rendition of PPO plastics flame retardant the aforegoing discussion is particularly applicable. Furthermore, it is important that, in addition to the retention of good physical characterstics, three characteristics (one of which is critical) of the product (PPO) be within certain limitations in order to provide a functional flame retarded product. These three characteristics are (1) light stability (as measured, for example, by Δ E color values, hereinafter defined), (2) flame retardancy (as measured, for example, by UL-94, hereinafter defined, and which is a critical characteristic and limitation), (3) thermal stability (as measured, for example, by certain ASTM tests for decomposition and migration, hereinafter defined). This characteristic of flame retardancy is not an arbitrary item but is a criteria which is strictly adhered to in the poly(phenylene oxide) art and hereinafter explained in more detail, with particular reference to the examples contained herein.

In conjunction with the foregoing discussion, the prior art in general suggests the use of halogen-containing materials as "potential" or "possible" flame retardants for plastic materials. However, the prior art also recognizes that any material must be adjudged or a case by case basis because of the unpredictable results of the end product when any additive is incorporated therein. For example, with reference to the use of a halogenated fire retardant in U.S. Pat. No. 3,658,634, attention is directed to the fact that the patentee specifically points out the disadvantages in the use of a halogen-containing fire retardant. In Column 1, lines 14-17, the patentee states: "Therefore, if it is possible to impart fire-retardancy to the thermoplastic polymers without deteriorating the useful properties of the thermoplastic polymers, they can be widely used in the field of inertia, construction and electric industries." In Column 1, lines 26-32, the patentee states: "--the compounds containing chlorine or bromine atoms to be used as fire-retardant agents, are generally sublimated and therefore, the fire retardant agents are sublimated and lost in the process for producing fire-retardant polymers or in after-finishing processes; accordingly, deteriorations of fire-retardancy or difficulties in use tend to occur more often than not."

In Column 1, lines 39-44 the patentee states: "--the compounds containing chlorine or bromine atoms to be used as fire-retardant agents are unstable in most cases when exposed to ultraviolet rays." In Column 1, lines 59-64 the patentee states: "However, as a matter of fact, only very few fire-retardant polymers can be used in actual practice although they are said to have fire-retardant effects, because there are restrictions such as the conditions employed in production attributable to the properties of the fire-retardant agent, or to the properties of the polymers into which they are to be incorporated."

It can be seen, then, from the foregoing discussion and quoted subject matter that the field of flame retardancy is highly sophisticated, unpredictable and requires substantial research to produce an end product (plastic composition) which meets the necessary criteria for utilization purposes, particularly under the present day government standards. Thus, there is always a demand for a material which will function as a flame retardant in PPO polymers and concurrently will not, by incorporation therein, adversely effect the chemical and/or physical and/or mechanical properties of the resultant PPO containing plastic composition (herein also referred to as "PPO plastic composition") and also have utility.

The prior art problem of providing a flame retarded PPO polymer composition having desired chemical, physical and mechanical properties, in addition to functional utility, has now been substantially solved by the present invention and the above-described disadvantages substantially overcome.

Accordingly, one of the main objects of the present invention is to provide PPO plastic compositions which are flame retarded.

Another object of the present invention is to provide a unique three component system for PPO plastic compositions which will not substantially adversely affect the chemical and/or physical and/or mechanical properties of said compositions.

A salient object of the present invention is to provide a PPO plastic composition which has certain defined flame retardancy property.

A further object of the present invention is to provide a flame retardant and an enhancing agent which are economical and easy to incorporate into PPO plastics without being degraded or decomposed as a result of normal blending or processing operations.

BRIEF DESCRIPTION OF THE INVENTION

It has been found that the foregoing objects can be obtained by the use of a unique three component system which consists of (a) a poly (phenylene oxide) polymer (hereinafter defined), (b) certain bis-phenoxy compounds (hereinafter defined), and (c) an enhancing agent (hereinafter defined) to subsequently provide flame retarded plastic compositions which exhibit outstanding chemical, physical and mechanical properties.

It is to be understood that the term "flame retarded" as used herein refers and is restricted to a limited definition and that is the reduction in flammability of the plastic composition which contains the three component system. The criticality of this flame retardancy is more specifically set forth herein, with particular reference being made to page 19 herein regarding UL 94 classification (sometimes referred to herein as "values").

DETAILED DESCRIPTION OF THE INVENTION

The particular class of bis-phenoxy compounds used in the present invention compositions have the formula ##STR2##

In Formula I above, Z is bromine, m and m' are each an integer having a value of 1 to 5 inclusive with the proviso that the total bromine content of said compound is 6 to 10 bromine atoms inclusive, and T is (1) a straight chain carbon group having from one to four carbon atoms and includes, without limitation, groups such as --CH₂ --; --(CH₂)₂ --; --(CH₂)₃ --; and --(CH₂)₄ --; and (2) a branched chain carbon group having from two to four carbon atoms and includes, without limitation, groups such as follows: ##STR3## and ##STR4##

It is to be understood that all the compounds falling within Formula I above and as heretofore defined are generically described herein as "bis-phenoxy" compounds.

Representative, but without limitation, of said bisphenoxy compounds are the following: ##STR5##

In general, the bis-phenoxy compounds are prepared by reacting a halogenated phenol with a halogenated alkane at elevated temperatures in the presence of a basic material such as alkali metal hydroxides, carbonates, bicarbonates, oxides and hydrides. The preferred alkali metals are potassium and sodium. Where one desires to increase, for example, ease of handling the reaction mass, solvents such ketones (e.g. acetone, methyl ethyl ketone, and methyl iso-butyl ketone), alcohols (e.g. methanol, ethanol, iso-propyl alcohol, butyl alcohol and glycols), or aqueous solvents (e.g. water, a mixture of water and alcohol and a mixture of water and ketone) can be employed. The desired end product i.e. the bis-phenoxy compound, can be recovered from the reaction mass via various methods known to those skilled in the art. Where the end product requires recovery via crystallization, various aromatic solvents, such as benzene, toluene, xylene, dichlorobenzene and the like, can be used.

Specifically, the bis-phenoxy compounds are prepared according to the following reactions: ##STR6##

In the above reaction, X is halogen, preferably bromine, and T is the same as herein defined.

The above reaction is conducted at temperatures ranging from the freezing point of the initial reaction mass to the boiling point hereof. Preferably the temperatures are from about 40° C to about 200° C and more preferably from about 50° C to about 175° C. It is to be understood that the reaction can be conducted under sub-atmospheric (e.g. 1/10-8/10 atmospheres) pressure. Preferably, the reaction is carried out at atmospheric pressure.

The above-described processes can be carried out with conventional, readily available chemical processing equipment. For example, a conventional glass-lined vessel provided with heat transfer means, a reflux condenser and a mechanical stirrer can be advantageously utilized in practicing any of the preferred embodiments of the invention described in preparing the bis-phenoxy examples set forth herein.

The amount of bis-phenoxy compound employed in the present invention compositions is any quantity which will effectively render, in conjunction with the enhancing agent, the PPO polymer containing composition flame retardant. In general, the amount used is from about 1% to 25% by weight, based on the total weight of the composition. Preferably, the amount employed is from about 1% to about 20% by weight. It is to be understood that any amount can be used as long as it does not substantially adversely effect the chemical and/or physical and/or mechanical properties of the end plastic composition. The amount utilized, however, is such amount which achieves the objectives described herein.

The second component of the three component system, and which is critical therefor, are certain compounds which when used with the bis-phenoxy compounds promote a cooperative effect therebetween and thus enhance the flame retardancy of the resultant plastic composition as compared to the flame retardancy of either one component used separately. These "enhancing agents" comprise the oxides and halides of groups IVA and VA of the Periodic Table, i.e. oxides and halides of antimony, bismuth, arsenic, tin, lead, germanium, e.g. antimony oxychloride, antimony chloride, antimony oxide, stannic oxide, stannic chloride, aresenous oxide, arsenous chloride, and the like; and organic and inorganic compounds of phosphorus, nitrogen, boron, and sulfur, e.g., triphenyl phosphate, ammonium phosphate, zinc borate, thiourea, urea, stannic sulfide, and the like and oxides and halides of titanium, vanadium, chromium, manganese, iron, niobium, molybdenum copper, zinc, magnesium, e.g., titanium dioxide, titanium chloride, vandanium pentoxide, chromic bromide, manganous oxide, molybdenum trioxide, ammonium molybdate; and hydrates of the above, e.g., stannic oxide hydrate, lead hydrate; and combinations thereof. The preferred enhancing agents are the oxides of antimony, arsenic and bismuth. However, any compound which on decomposition, as by ignition, yields these oxides would be suitable. Thus some organic antimonates are preferred. The enhancing agents disclosed in U.S. Pat. No. 3,205,196 are also suitable for use.

U.S. Pat. No. 3,205,196, column 2, states that "Antimony oxide is the antimony compound that is presently preferred for use in the present invention. However, many antimony compounds are suitable, inorganic antimony compounds include antimony sulfide sodium antimonite, potassium antimonite, and the like. Many organic antimony compounds are suitable such as the antimony salts of organic acids and their pentavalent derivatives disclosed in copending application Ser. No. 688,143, filed Oct. 4, 1957, now U.s. Pat. No. 2,996,528. Compounds of this class include antimony valerate, antimony caproate, antimony heptylate, antimony caprylate, antimony pelargonate, antimony caprate, antimony cinnamate, antimony anisate, and their pentavalent dihalide derivatives. Likewise the esters of antimonous acids and their pentavalent derivatives disclosed in copending application Ser. No. 688,108, filed Oct. 4, 1957, now U.S. Pat. No. 2,993,924, such as tris(n-octyl) antimonite, tris(2-ethylhexyl) antimonite, tribenzyl antimonite, tris(β-chloroethyl)antimonite, tris(β-chloropropyl) antimonite, tris(β-chlorobutyl) antimonite and their pentavalent compound are the cyclic antimonites such as trimethylolpropane antimonite, pentaerythritol antimonite, and glycerol antimonite. The corresponding arsenic and bismuth compounds can also be employed."

It is to be understood that such patents as U.s. Pat. No. 3,205,196; U.S. Pat. No. 2,996,528 and U.S. Pat. No. 2,993,924 are to be considered as incorporated herein by reference for all intents and purposes. Without limitation, preferred enhancing agents include Sb₂ O₃, SbCl₃, SbBr₃, SbI₃ SbOCl, As₂ O₃, ZnBO₄, BaB₂ O₄ ·H₂ O, 2·ZnO·3B₂ O₃·3·5 H₂ O and stannic oxide hydrate. The more preferred enhancing agent is antimony troixide.

The amount of enhancing agent employed in the present invention compositions is any amount which when used with said bis-phenoxy compounds will promote a cooperative effect therebetween. In general, the amount employed is from about 0.5% to about 15%, preferably from about 0.5% to about 10%, by weight, based on the total weight of plastic composition. Higher or lower amounts can be used as long as the desired end result is achieved.

The third critical component of the three component system is the poly(phenylene oxide) polymer (PPO). It is to be understood that the term poly(phenylene oxide) as used herein means products of the oxidative polymerization of phenols to poly(oxy phenylenes) which are also known as poly(phenylene oxides) or poly(phenylene ethers). The PPO polymer and methods of preparing the same are disclosed in detail, but without limitation, in the Encyclopedia of Polymer Science and Technology, "Phenols, Oxidative Polymerization", Vol. 10, pages 92-110, Interscience Publishers, New York (1969); this publication is to be considered as incorporated herein by reference. This term also includes blends with other thermoplastics and/or plasticizers, e.g. polystyrene; however, the poly(phenylene oxide) comprises in all cases at least 50% by weight of the blend.

Thus the poly(phenylene oxide) polymer used in the present inventin compositions is any poly(phenylene oxide) polymer herein defined and which one so desires to flame retard. It is to be understood that the poly(phenylene oxide) polymer used can be a "virgin" material, i.e. substantially free of additives such as stabilizers, plasticizers, dyes, pigments, fillers, and the like, or the poly(phenylene oxide) polymer can have additives (such as those mentioned and described herein) already contained therein or added concurrently with or after the addition of the bis-phenoxy compounds and enhancing agents.

The bis-phenoxy compounds and enhancing agents can be incorporated into the poly(phenylene oxide) at any processing stage in order to prepare the present invention plastic compositions. In general, this is undertaken prior to fabrication either by physical blending or during the process of forming poly(phenylene oxide) per se. Where one so desires, the bisphenoxy compounds and/or enhancing agents may be micronized into finely divided particles prior to incorporation into the poly(phenylene oxide).

It is also within the scope of the present invention to employ other materials in the present invention compositions where one so desires to achieve a particular end result. Such materials include, without limitation, adhesion promotors; antioxidants; antistatic agents; antimocrobials; colorants; flame retardants such as those listed on pages 456-458, Modern Plastics Encyclopedia, ibid, (in addition to the new class of flame retardants described herein); heat stabilizers; light stabilizers; pigments; plasticizers; preservatives; ultraviolet stabilizers and fillers.

In this latter category, i.e. fillers, there can be mentioned without limitation, materials such as glass; carbon; cellulosic fillers (wood flour, cork and shell flour); calcium carbonate (chalk, limestone, and precipitated calcium carbonate); metal flakes; metallic oxides (aluminum, beryllium oxide and magnesia); metallic powders (aluminum, bronze, lead, stainless steel and zinc); polymers (comminuted polymers and elastomerplastic blends); silica products (diactomaceous earth, novaculite, quartz, sand, tripoli, fumed colloidal silica, silica areogel, wet process silica); silictes (asbestos, kaolimite, mica, nepheline syenite, talc, wollastonite, aluminum silicate and calcium silicate); and inorganic compounds such as barium ferrite, barium sulfate, molybdenum disulfide and silicon carbide.

The above mentioned materials, including fillers, are more fully described in Modern Plastics Encyclopedia, ibid, and which publication is incorporated herein (in toto) by reference.

The amount of the above described materials employed in the present invention compositions can be any quantity which will not substantially adversely effect the desired results derived from the present invention compositions. Thus, the amount used can be zero (0) percent, based on the total weight of the composition, up to that percent at which the composition can still be classified as a plastic. In general, such amount will be from about 0% to about 75% and more specifically from about 1% to about 50%.

With reference to the present invention plastic compositions described herein, one of the critical features thereof is the unusually high flame retardancy thereof. The significance of flame retardancy of plastic compositions is well recognized in the art as heretofor mentined. However, recent developments in conjunction with the use of flame retardant plastic compositions as judged by the Consumer Product Safety Commission, require a UL-94 (hereinafter discussed) of V-O in order to produce a commercially acceptable article of manufacture. The Consumer Product Safety Commission is continuing to set mandatory standards in the field where the plastic compositions are utilized and since about 1970 have increased the criticality of the UL value of plastic compositions. In reacting to the Consumer Product Safety Commission's mandatory standards in this area, the producers of (plastic composition) articles of manufacture are now requiring that said articles have a V-O value in order to meet new mandatory standards which are anticipated to be activated by federal legislature shortly. Thus, the significance of a plastic composition having a V-O value is well recognized in the art; note MODERN PLASTICS, Sept. 1974, pages 74-77, Dec., 1974, page 20, and Dec., 1975, pages 42-44, 48-50 and 59, and which publications are to be considered as incorporated herein by reference.

In conjunction with the present invention plastic compositions described herein, an important feature thereof is the light stability thereof. The significance of light stability of plastic compositions is recognized in the art, e.g. the publication entitled "The Measurement of Appearance" by Mr. Richard S. Hunter (Hunter Associates Laboratory, Inc., 9529 Lee Highway, Fairfax, Virginia) 1973. Mr. Hunter has been associated with the efforts of defining appearance and color since the 1930's and was for many years an associate of Gardner who is another authority in this field. The following paragraphs from Mr. Hunter's book are set forth in order to demonstrate this light stability significance.

The Judd-Hunter system "of scales for color difference was based on Judd's uniform chromaticity scales triangle. Judd made an instrumental study of a number of woolen swatches rated by dyers for their acceptability as commercial color matches to standard. The NBS unit of color difference was designed by Judd to be the maximum difference commercially acceptable in the textile trade as represented by these dyers at the time when the study was carried out (Judd, 1939). The NBS Unit generally referred to today is not Judd's 1939 unit, but the Hunter 1942 version of the Judd unit with 100 units falling between black and white."

"Since 1942 this unit has been used in terms of a number of the opponent color scales. In a color scale which is already uniform in its visual spacing of lightness and chromaticity, and which has 100 units between black and white as well as rectangular coordinates for chromaticity, color difference in approximate NBS units can be specified in units of that system. The color difference becomes the distance between the two colors in that color spce. With rectangular coordinates, the formula is:

    Δ E=√ΔL.sup.2 + Δa.sup.2 + Δb.sup.2

Similarly if only the chromaticity component of difference is desired, the formula is:

    Δ C = √Δa.sup.2 +Δb.sup.2

"Following Judd's proposed unit of color difference, Hunter proposed the measurement of much the same quantity by a photoelectric tristimulus method in 1942. In the next year, Scofield proposed a quantity which was quite a bit easier to compute. Scofield used the reciprocal of the square root of reflectance instead of the reciprocal of the fourth root of reflectance as a multiplier in adjusting reflectance values for uniform lightness scale intervals. This is the only difference between the Scofield and the Judd-Hunter formulas for color difference. (Scofield, 1943)."

"In 1948, Hunter started to develop a tristimulus instrument which would read chromaticity dimensions of opponent colors directly. He was seeking to improve the precision and usefulness of results of the tristimulus reflectometers previously used. The R_(d) scales developed in the period 1948 and 1950 did not have a uniform lightness readout but did have direct reading visually uniform a and b scales. The L scales, in which there is approximate perceptual uniformity in all three dimensions, were created in the period 1950-1952 but were not described in a formal publication until 1958. These two sets of Hunter Color Difference Meter scales enjoy wide use because of the fact that they can be read directly from a tristimulus instrument with high precision, and offer instrumental computation of color difference by the ΔE formula given above."

"NBS Unit of Color Difference is defined as: the unit of color difference of the National Bureau of Standards. The unit is about four times as great as the smallest difference observable under ideal conditions. Differences of less than one unit are usually not important in commercial transactions. In Munsell terms, one NBS unit is equivalent to about 0.1 Value step, 0.15 Chroma step, or 2.5 Hue step at Chroma 1."

"Hunter further investigated the use of L', α', β' for color difference measurement. He recognized at this time (which no other color-difference scale before or since has recognized) that perceived color difference will depend on the proximity of the specimens compared and on their glossiness. Accordingly, the 1942 Hunter color difference equation includes factors to account for these variables. It is this equation, with selected constants, that defines the widely used NBS unit of color difference."

"High precision is almost always essential for useful color difference measurements. Only with precise instruments is it possible to measure color difference as small as those the eye can see. Instrument accuracy is also normally a requisite because spectrally inaccurate instruments, even though precise, will give visually inaccurate color difference measurements wherever there are spectral differences between the specimens involved. The ease of obtaining and interpreting values of color difference is another factor which may affect the selection of a procedure."

"Twenty years ago, color difference scales were in demand to serve as a basis for setting one-number tolerances for fading and acceptability of matches. The Index of Fading and NBS unit were used as units."

"Today, the concept of color difference is more refined. One number tolerances are seldom used. Instead, color difference tolerances are designed as boundaries in color space within which acceptable colors must fall. The boundaries do not necessarily correlate with perceptibility of difference but rather with the limits of acceptability. The standard color, furthermore, may not be in the center of the bounded region but may be displaced to one side. For example, where subsequent yellowing may occur, the tolerance for the yellow-blue dimension might be +0.1, -0.8 units."

"Color difference specifications are tighter today and tolerances are smaller. The specification usually treats the color dimensions separately so that a complete specification would contain nine members: The three numbers that describe the desired color, and the six numbers that describe the individual plus and minus tolerances. Such tolerances can be reduced to graphs which not only show acceptability that provide a guide to the formulation correction needed to correct an off shade. When the question of acceptability becomes a question of sorting objects according to shade, a graphical chart showing the classification of color values can be quite helpful."

"Although color measurements are frequently used for identification, sorting and recording of color values, the primary uses of tristimulus instruments all involve measurements of fairly small color differnces. The most frequent uses of these small color difference measurements are to establish closeness to standard and to give guidance for the adjustment of color mismatches. They are also used in the study of deterioration in a product as a result of exposure and use."

"Spectrophotometers and tristimulus instruments made up the majority of color appearance measuring instruments in use in industry. Spectrophotometers give wavelength-by-wavelength analyses of the reflecting properties of objects, while tristimulus instruments by the use of filters which approximate the Standard Observer functions of the eye, give measurements of color in X, Y, Z terms, or in L, a, b values. Spectrophotometers are essential where color formulation is involved, and metamerism must be controlled. However, tristimulus colorimeters and reflectometers provide precise and less expensive means for the routine measurement of color and adjustment of small color difference."

In view of the foregoing quoted subject matter, it can thus be seen that a change in ΔE value of 1 unit constitutes a real change. Note also Japanese patent application (publication 022,456 of 1974) which shows that achieving a color change in ΔE of only 2.3 is significant as it pertains to a polycarbonate polymeric composition; (this value is substantially the same as those ΔE values obtained in polycarbonate tests and which results thereof are shown in Table X herein, i.e. 2.3 versus 2.5 over the control). Both of these publications (i.e. the Japanese patent 022,456 and the Hunter book) are to be considered as incorporated herein by reference. It is to be noted also that a lower ΔE value is more desired and the higher ΔE value is least desired. This ΔE value is not an abstract value, however, since one must compare it with the ΔE values of the "control" plastic composition. One of the desired ΔE values would be where both the ΔE values of the "control" plastic composition (without additives-i.e. without flame retardant and enhancing agent) and the plastic composition with said additives are substantially the same or the latter has a lower value.

EXAMPLE I

A poly(phenylene oxide) (PPO) plastic material, (GE 523-801, a product of General Electric Company and containing substantially no fillers) is utilized as the base resin in order to prepare 8 formulations (plastic compositions). With the exception of formulation No. 1, the particular bis-phenoxy compound (and the antimony trioxide enhancing agent were indicated) is incorporated into the plastic by adding both to a Brabender mixer ("Plastic-Corder", Torque Rheometer, Model PLV-150, C. W. Brabender Instruments Inc., South Hackensack, N.J.). The mixer is equipped with a pair of roller type blades positioned within a head provided with heat transfer means.

The resultant mixture is heated to about 320° C; at this temperature, it is in a molten state. The percentages by weight of each component utilized in the respective formulations are listed in Table I. Each formulation is discharged from the mixer and upon cooling solidifies and is ground into chips. The chips are subjected to compression molding in a Wabash press by placing said chips between two platens, the bottom of which contains four equal size depressions three inches by five inches by 1/8 inch deep. The top platen is then placed over the bottom platen and heat transfer means supplied thereto in order to melt said chips and thus provide solid samples (after cooling) for testing.

Portions of the solid samples of each respective formulation (Nos. 1-9) prepared according to the above described procedure are then subjected to two different standard flammability tests, i.e. UL 94 and ASTM D-2863-70. The UL 94 is, in general, the application of a burner to a test specimen (strip) for a certain period of time and observation of combustion, burning, and extinguishment. This procedure is fully set forth in Underwriters' Laboratories bulletin entitled UL 94, Standard for Safety, First Edition, September 1972 and which is incorporated herein by reference. ASTM No. D-2863-70 is a flammability test which correlates the flammability of a plastic specimen to the available oxygen in its immediate environment; this correlation is stated as an Oxygen Index, O.I., level predicated upon the percent oxygen in the gaseous medium which is required to just provide a steady state of continuous burning of the plastic specimen. This ASTM method is fully described in 1971 Annual Book of ASTM Standards - Part 27, published by the American Society for Testing and Materials, 1916 Race Street, Philadelphia, Pa.; this publication is to be considered as incorporated (in toto) herein by reference. The UL 94 test is the more critical test as it is the test generally used to determine the suitability of thermoplastics for commercial applications.

The results of these flammability tests are shown in Table I.

                                      TABLE I     __________________________________________________________________________     FLAMMABILITY DATA FOR PPO PLASTIC COMPOSITIONS     CONTAINING BIS-PHENOXY COMPOUNDS WITH AND WITHOUT ENHANCING AGENTS     FORMULATION               BIS-PHENOXY COMPOUND                               ENHANCING AGENT                                            OXYGEN INDEX     NO.       FORMULA  %      Sb.sub.2 O.sub.3                                       %    %         UL 94     __________________________________________________________________________     1.        --       0              0    25.5      SB     2.        III      10             0    30.0      SE-O     3.        III      10             3    33.5      SE-O     4.        III      13             3    33.0      SE-O     5.         II      5              3    28.5      SE-O     6.         II      10             0    29.0      SE-O     7.         II      10             3    32.0      SE-O     8.         II      16             3    36.0      SE-O     9.        III      5              0    28.0      SE-1     __________________________________________________________________________

Referring to Table I, the bis-phenoxy compound formula II or III relates to the structural formulae heretofor set forth; and the UL 94 values are on a graduated scale wherein the highest degree to lowest degree of flame retardancy is respectively SE-0, SE-1, SE-2, SB and Burns.

The results shown in Table I demonstrate the unique effectiveness of of the plastic composition containing PPO, the bis-phenoxy compound and the enhancing agent. Specifically, formulation No. 1 (the control ) had a O.I. of 25.5 and UL 94 value of SB. Nos. 2, 6 and 9 show only the use of the particular bis-phenoxy compound without an enhancing agent; No. 9 had a UL 94 value of SE-1. Thus at this lower level of using the bis-phenoxy compound, i.e. No. 9, the critical SE-0 was not obtained.

The use of the three component system, i.e. PPO, bis-phenoxy compound and enhancing agent, is fully demonstrated via the results obtained from testing formulation Nos. 3, 4, 5, 7 and 8. Thus, the use of an enhancing agent such as Sb₂ O₃ to promote a cooperative effect between such agent and the bis-phenoxy compound is quite apparent particularly when viewing the results obtained from testing formulation Nos. 1 and 9. The highest UL 94 ratings are obtained in all cases with the three component system.

EXAMPLE II

Portions of the solid samples of Formulation Nos. 1, 3, 5, 7 and 8 prepared according to the above described procedure of Example I are subjected to the following ASTM tests in order to ascertain other properties of the resultant plastic composition:

    ______________________________________     (1)  Tensile Strength          (at break)      :     ASTM Test No. D638-61T;     (2)  Flexural Strength                          :     ASTM Test No. D790-63;     (3)  Flexural Modulus                          :     ASTM Test No. D790-63;     (4)  Flexural Modulus                          :     ASTM Test No. D256-56; and     (5)  Heat Distortion          Temperature (HDT)                          :     ASTM Test No. D648-56.     ______________________________________

Each of the aforementioned ASTM Tests are standard tests in the art and are utilized collectively in order to ascertain the efficacy of a polymeric system as an overall flame retarded composition for commercial application. All of these ASTM Tests are to be considered as incorporated herein by reference.

The results of these ASTM tests show that the physical properties of the present invention compositions are basically the same (except O.I. and UL 94 values) as the plastic material without the flame retardant (i.e. formulation No. 1). Thus, there is no substantial adverse effect on the physical properties of the plastic material when the bis-phenoxy compounds and enhancing agents are incorporated therein. The results of these ASTM tests are shown in Table II.

                                      TABLE II     __________________________________________________________________________     Properties of PPO Plastic Compositions     Containing Various Additives                Tensile                     Flexural                          Flexural                               Notched Izod                Strength                     Strength                          Modulus                               Impact  HDT O.I.     Formulation                psi  psi  10.sup.5 psi                               ft.lb/in.                                       ° F                                           %   UL 94     __________________________________________________________________________     1) No. 1 (control)                12,000                     16,000                          3.7  1.0     345 25.5                                               SB     2) No. 3   11,800                     15,450                          3.6  1.0     33.5                                           SE-O     3) No. 5   11,500                     15,100                          3.6  0.9     340 28.5                                               SE-1     4) No. 7   10,950                     14,600                          3.5  1.0     332 32.0                                               Se-O     5) No. 8   10,650                     14,050                          3.5  0.8     329 36.0                                               SE-O     __________________________________________________________________________

Referring to Table II, it is readily demonstrated that the physical properties of the present invention composition (e.g. formulation Nos. 3, 5, 7 and 8) are basically the same (except O.I. and UL 94 values) as the PPO material without the bis-phenoxy compound (i.e. formulation No. 1). In view of the results set forth in Table II, it can be seen then that no adverse effect on physical properties via such use of the bis-phenoxy is realized.

Thus, the uniqueness and superiority of the present invention compositions is quite apparent.

EXAMPLE III

The procedure of Examples I and II are repeated except that the bis-phenoxy compound used corresponds to Formula IV, heretofor set forth, instead of Formulae II and III. Substantially the same results are obtained using the Formula IV compound as those obtained using Formulae II and III compounds.

EXAMPLE IV

The procedure of Examples I, II and III are repeated except that the enhancing agent used is zinc borate instead of Sb₂ O₃. Substantially the same results are obtained using zinc borate as those obtained using Sb₂ O₃.

EXAMPLE V

Strip samples of each of formulations Nos. 1 (control), 3, 5, 7 and 8, Table I, are subjected to light stability tests via the use of a "Weather-Ometer", model 25/18 W.R., Atlas Electrical Devices Company, Chicago, Illinois. Utilizing an operating temperature of 145° F and a 50% relative humidity, each strip is subjected to 200 hours of "simulated daylight" via the use of a carbon arc. The results show that after 200 hours, there is no significant discoloration in any strip tested and which demonstrates that the present invention compositions are highly resistant to deterioration by light.

EXAMPLE VI

Samples of each of formulation Nos. 1 (control), 3, 5, 7 and 8, Table I, are subjected to temperature (thermal) stability tests via the use of thermal gravimetric analysis (TGA). This test employed the use of a "Thermal Balance", model TGS-1, Perkin-Elmer Corporation, Norwalk, Connecticut, and an electrical balance, Cahn 2580 model, Cohn Instrument Company, Paramount, California. The results of these tests show that the bis-phenoxy compound containing formulations had more than adequate stability for melt processing and subsequent heat aging (i.e. high temperature applications) and thus demonstrating that the particular bis-phenoxy compounds are quite compatible with the PPO material. The bisphenoxy compound stability thus aids in providing sufficient flame retardancy at the PPO decomposition temperature. This test also demonstrates that the bis-phenoxy compounds do not exhibit migration.

COMPARATIVE EXAMPLES

The following examples are presented to demonstrate the unpredictability of plastic compositions, via the end results, containing the same bis-phenoxy compounds, with or without an enhancing agent.

Referring more specifically to the following examples, Example VII compares a three component system, i.e. ABS, certain "bis-phenoxy compounds" (herein referred to as BPC), and enhancing agent with four other polymers containing the same bis-phenoxy compounds (as used in the present invention) and enhancing agent. The four comparative polymers are polyacrylonitrile, polypropylene, nylon and polymethylmethacrylate. As will be seen from the results hereinafter set forth, the four other polymers had no flame retardant efficacy when incorporating the bis-phenoxy compounds and enhancing agents, whereas the ABS system did and so demonstrated an unexpected and substantial flame retardant efficacy. These results, thus, are another indication of the unpredictability of additives when incorporated into polymer systems and correspond to the subject matter set forth in "Modern Plastic Encyclopedia", ibid., regarding the use of octabromobiphenyl in one polymer but not shown for use (or functionally equivalent) in numerous other materials.

Referring to Example VIII, this example sets forth the comparison of the use of the bis-phenoxy compounds in eight polymer systems but in substantially more detail with particular reference to light stability, flammability and thermal stability. The results disclosed in this Example VIII are similar to those results ovtained in Example VII.

EXAMPLE VII

Regarding Formulation Nos. 1 - 10 in Table III, a virgin polyacrylonitrile plastic material, (T-61 polymer crumb, a product of American Cyanamid and characterized as a copolymer of 93% by weight acrylonitrile and about 7% by weight methyl methacrylate) is utilized as the base resin in order to prepare 10 formulations (plastic compositions). With the exception of formulation No. 1, the particular bis-phenoxy compound (and the antimony trioxide enhancing agent where indicated) is incorporated into the plastic (which is dried to remove moisture therefrom) by adding both to a Waring blender which contains acetone as a dispersing liquid. The resultant mixture, after blending for 3 minutes, is poured into evaporation dishes and the acetone evaporated, first at room temperature (20°-25° C) for 60 minutes and followed by oven drying at 60° C for one hour.

The percentages by weight of each component utilized in the respective formulations are listed in Table III. Each formulation is discharged from the evaporation dish and is ground into powder. The powder is subjected to compression molding in a Wabash press by placing said powder between two platens, the bottom of which contains four equal size depressions three inches by five inches by 1/8 inch deep. The top platen is then placed over the bottom platen and heat transfer means supplied thereto in order to melt said powder and thus provide solid samples (after cooling) for testing. The temperature and ram pressure utilized are respectively 100° C and 30 tons.

A polypropylene plastic material, (Hercules Pro-fax® 6523 grade of polypropylene) is utilized as the base resin in order to prepare 13 formulations (plastic compositions) - Nos. 11-23 shown in Table III. With the exception of formulation No. 11, the particular bis-phenoxy compound (and the antimony trioxide enhancing agent where indicated) is incorporated into the plastic and solid samples prepared according to the procedure set forth in Example I.

A virgin nylon 6 plastic material, (Zytel® 211, a product of E. I. du Pont de Nemours and Co., Wilmington, Delaware) is utilized as the base resin in order to prepare 7 formulations (plastic compositions) - Nos. 24-30 shown in Table III. With the exception of formulation No. 24, the particular bis-phenoxy compound (and the anitmony trioxide enhancing agent where indicated) is incorporated into the plastic and solid samples prepared according to the procedure set forth in Example I.

Regarding Formulation Nos. 31-33 in Table III, a virgin polymethylmethacrylate plastic material, Plexiglas® V (811) a commercially available product of Rohm and Haas Company, Philadelphia, Pennsylvania and being substantially free of additives, is utilized as the base resin in order to prepare 3 formulations (plastic compositions). With the exception of formulation No. 31, the particular bis-phenoxy compound (and the antimony trioxide enhancing agent where indicated) is incorporated into the plastic and solid samples prepared according to the procedure set forth in Example I.

Referring to Formulation Nos. 34-37 in Table III, an acrylonitrile-butadiene-styrene (ABS) polymer plastic material, Marbon TP-2098, a product of Marbon Division, Borg-Warner Corporation, Washington, West Virginia, and which is a slight process variation of their commercially available "T" grade ABS polymer, is utilized as the base resin in order to prepare four (4) formulations (plastic compositions). These formulations, Nos. 34-37, are prepared in accordance with the procedure described in ASTM D-1897-68.

Portions of the samples of each respective formulation (Nos. 1-37, Table III) prepared respectively according to the above described procedures are then subjected to two different standard flammability tests, i.e. UL 94 and ASTM D-2863-70, i.e. Oxygen Index, O.I.

The results of these flammability tests are shown in Table III.

                  TABLE III     ______________________________________     FLAMMABILITY DATA FOR DIFFERENT PLASTIC COMPOSITIONS     CONTAINING BIS-PHENOXY COMPOUNDS WITH AND     WITHOUT ENHANCING AGENTS     ______________________________________            BIS-        ENHAN-     FORMU- PHENOXY     CING      OXYGEN     LATION COMPOUND    AGENT     INDEX   UL 94     NO.    FORMULA %   Sb.sub.2 O.sub.3, %                                  %       VALUE     ______________________________________     Polyacrylonitrile Polymer     1.     --        0     0       22.5    SB     2.     III       2     0       23.5    SB     3.     III       5     0       23.8    SB     4.     III       10    0       24.0    SB     5.     III       5     5       25.3    SB     6.     III       5     10      25.3    SB     7.     II        2     0       23.0    SB     8.     II        5     0       23.0    SB     9.     II        10    0       24.0    SB     10.    II        5     5       25.0    SB     Polypropylene Polymer     11.    --        0     0       18.0    Burns     12.    III       15    0       20.0    SB     13.    III       15    5       22.8    SB     14.    III       25    0       26.0    SB     15.    III       25    5       24.0    SB     16.    III       25    5       26.0    SB     17.    II        15    0       19.0    SB     18.    II        15    5       22.0    SB     19.    II        20    5       25.0    SB     20.    II        25    0       23.0    SB     21.    II        25    5       25.0    SB     22.    III       20    10      25.0    SB     23.    II        20    10      24.0    SB     Nylon     24.    --        0     0       23.0    SB     25.    III       10    0       23.5    SB     26.    III       10    3       24.5    SB     27.    III       13    3       27.5    SE-2     28.    II        10    0       23.5    SB     29.    II        10    3       24.0    SB     30.    II        13    3       27.0    SE-2     Polymethylmethacrylate Polymer     31.    --        0     0       18.0    SB     32.    II        15    0       20.5    SB     33.    II        15    5       20.5    SB     Acrylonitrile-Butadiene-Styrene (ABS) Polymer     34.    --        0     0       19.0    HB(SB)     35.    II        15    0       27.0    HB(SB)     36.    II        15    5       32.5    V-O                                            (SE-0)     37.    III       15    5       35.0    V-0                                            (SE-0)     ______________________________________

Referring to Table III, the bis-phenoxy compound formula II and III relates to the structural formulae heretofor set forth; and the UL 94 values are on a graduated scale wherein the highest degree to lowest degree of flame retardancy is respectively SE-0 (V-0), SE-1 (V-1), SE-2 (V-2), SB (HB) and Burns.

The results shown in Table III demonstrate the unexpected and completely unpredictable results using different polymer systems, in this instance the unique effectiveness of the plastic composition containing a three component system which consists of the bis-phenoxy compounds, an enhancing agent and acrylonitrile-butadiene-styrene (ABS) polymer as compared to the use of such bis-phenoxy compound with or without an enhancing agent in a polyacrylonitrile polymer, a polymethylmethacrylate polymer, a nylon polymer and a polyolefin such as polypropylene polymer, the latter four of which polymers show substantially no increase in flame retardancy via the use of said bis-phenoxy compounds with or without an enhancing agent.

Regarding the use of an enhancing agent in formulation Nos. 5 and 6, the results obtained therefrom show that there is no increase in flame retardance. Thus, for example, No. 1 (control) has an UL value of SB and Nos. 5 and 6 (which have different enhancing agent levels, 5% versus 10%) have also an UL value of SB. In viewing the results of No. 3 (5% - 0%) and No. 5 (5% - 5%), it can be seen that even the use of the enhancing agent does not increase flame retardancy in a polyacrylonitrile polymer.

With reference to the polypropylene polymer compositions Nos. 11 thru 23, it can readily be seen from the UL 94 values that the incorporation of the particular bis-phenoxy compound therein resulted in substantially little, if any, increase in flame retardancy as compared to the control, considering the experimental accuracy. Even the use of an enhancing agent did not result in an increase in flame retardancy, note No. 12-SB and No. 13-SB. Predicated upon this data, it is thus seen that the incorporation of the bis-phenoxy compounds (with or without an enhancing agent) in a polypropylene results in no flame retardant efficacy.

Specifically referring to the nylon polymer compositions Nos. 24-30, formulation No. 24 (the control) had an UL value of SB. In Nos. 25 and 28, the use of the particular bis-phenoxy compound results in no increase in flame retardancy via incorporation of 10% (SB versus SB) of the bis-phenoxy compound per se.

Regarding the use of an enhancing agent in formulation Nos. 26, 27, 29 and 30, the results obtained therefrom show there is substantially little, if any, increase in flame retardancy. Thus, for example, No. 1 (control) has an UL value of SB and Nos. 26 and 29 also have an UL value of SB. While Nos. 27 and 30 each have an UL value of SE-2, this is not considered a significant increase and thus even the use of the enhancing agent does not result in flame retardancy efficacy.

With reference to the polymethylmethacrylate polymer compositions Nos. 31, 32 and 33, it can readily be seen from the UL values, i.e. all SB, that the incorporation of the particular bis-phenoxy compound therein results in no increase in flame retardancy as compared to the control. Even the use of an enhancing agent did not result in an increase in flame retardancy. Consequently, it can readily be seen that the incorporation of the bis-phenoxy compounds in a polymethylmethacrylate results in no flame retardant efficacy.

The most unexpected results in flame retardancy were obtained via the incorporation of the particular bis-phenoxy compounds and enhancing agents in an acrylonitrile-butadiene-styrene (ABS) polymer. Referring specifically to formulation Nos. 34 and 37, the control, formulation No. 34, had an UL value of HB(SB). Notwithstanding the incorporation of 15% (No. 35) of the particular bis-phenoxy compound per se in the ABS polymer, there still results an UL value of SB. Use of the enhancing agent with both bis-phenoxy compounds formulae II and III, in formulation Nos. 36 and 37 results in an unexpected UL value change from SB (No. 35) to SE-0 (No. 36) and SE-0 (No. 37). In view of these results, it was quite unexpected that the ABS polymer system, having incorporated therein the particular bis-phenoxy compounds and enhancing agent would show such superior flame retardant efficacy based on the results obtained from the performance of the other four (4) polymers, i.e. polyacrylonitrile, polypropylene, nylon and polymethylmethacrylate polymer systems having the same bis-phenoxy compounds and enhancing agents incorporated therein. Consequently, it can readily be seen that it is not possible to predict the efficacy and/or functionality of any halogen-containing material (which may be suggested as a flame retardant) in any polymeric system until one actually conducts a substantial research program thereon and ascertains certain properties of the "flame retarded" system and its utility.

EXAMPLE VIII

Solid samples of eight different plastic compositions separately containing certain prior art compounds and the herein described bis-phenoxy compound, both with or without the herein described enhancing agents, are prepared according to the above described ABS procedure of Example VII, except that the specimens are injection molded instead, rather than compression molded, and are subjected to the following tests in order to ascertain comparative properties of the resultant plastic compositions:

    ______________________________________     (1)  Flammability          (a) Oxygen Index, O.I.                          :     ASTM Test No. D-2863-70          (b) UL-94       :     UL-94 Procedure described                                herein and dated February 1,                                1974.     (2)  Light Stability          (Weather Ometer)                          :     Procedure described herein          (a) Visual rank       and in Example V, except          (1 is the highest)    that the light source is the          (b) Gardner Colorimeter                                Xenon arc rather than a          ("ΔE" Values)   carbon arc.     (3)  Initial Color   :     Visual color observation                                immediately after injection                                molding.     (4)  Visual Migration                          :     Visual observation of sur-                                face haze presence.     (5)  TGA and Isotherm                          :     Procedure described in                                Example VI.     (6)  Melt Flow       :     ASTM Test No. 1238-70.     (7)  Notched Izod Impact                          :     ASTM Test D256-72a; and     (8)  Heat Distortion          Temperature (HDT)                          :     ASTM Test No. D648-72.     ______________________________________

Regarding item (2) above, i.e. light stability, the results obtained via the "Visual" rank include any color changes which occurred in the molded materials tested from a combination of processing and exposure to the xenon arc.

Each of the aforementioned Tests are standard tests in the art and are utilized collectively in order to ascertain the efficacy of a polymeric system as an overall flame retardant composition for commercial application. All of these tests are to be considered as incorporated herein by reference.

The different polymers utilized along with trade names and corresponding suppliers are listed below.

    ______________________________________      Polymer      Trademark    Supplier     ______________________________________     ABS          Cycolac T-2098                               Borg-Warner     Polystyrene  Bakelite TMDE-                               Union Carbide     (high impact) HIPS                  6500     Polycarbonate                  Lexan 141    General Electric     Nylon 6      Zytel 211    DuPont     Polypropylene                  Profax 6523  Hercules     Terephathalate poly-                  Valox 310    General Electric     ester     Polyphenylene oxide,                  Noryl 731    General Electric     modified (PPO)*     Polyethylene,                  Bakelite DPD-                               Union Carbide     Low Density (LDPE)                  3900     ______________________________________      *Present Invention Polymer System

The concentration of the additives (i.e. prior art compounds --designated PAC--or certain bis-phenoxy compounds --designated BPC -- with or without an enhancing agent --designated EA--and the respective Table Nos. listing the pertinent data are shown below. The Table numbers are shown in parenthesis.

    ______________________________________                    PAC or BPC/EA-     Polymer        Sb.sub.2 O.sub.3 %                                 PAC or BPC ONLY     ______________________________________     ABS            15/5(IV)     20/0(V)                                 + 30/0(VI)     HIPS           12/4(VIII)   16/0(VIII)                                 + 30/0(IX)     Polycarbonate  3/1(X)     Nylon          12/4(XI)     Polypropylene  12/4(XII)     Polyester      12/4(XIII)   16/0 (IV)     PPO (Present Invention                    9/3 (XV)     Polymer     PPO (Present Invention                    9/3 Pigmented     Polymer        TiO.sub.2 (XVI)     LDPE           20/5(XVII)     ______________________________________

All percentages (%) shown are on a weight basis, based on the total weight of the plastic composition.

The identification of the prior art compound (PAC) listed as A,B,C,D,E and F in the Tables are shown below:

    ______________________________________     PAC     (Let-     ter) FORMULA     ______________________________________     A    C.sub.6 Cl.sub.5 C.sub.6 Cl.sub.5          decachlorobiphenyl     B    C.sub.6 Br.sub.5 OC.sub.6 Br.sub.5          Bis-(pentabromophenyl)ether     C    C.sub.6 Br.sub.6          Hexabromobenzene     D    C.sub.6 Br.sub.5 CH.sub.2 Br          Pentabromobenzyl bromide     E    C.sub.6 H.sub.2 Br.sub.2 (OCH.sub.3)C(CH.sub.3).sub.2 C.sub.6          H.sub.2 Br.sub.2 (OCH.sub.3)          Bis-2,2-(3,5-dibromo-4-methoxyphenyl)propane     F    C.sub.6 H.sub.2 Br.sub.3 OCH.sub.2 CBr=CBrCH.sub.2 OC.sub.6 H.sub.2          Br.sub.3          Trans 1,4-Bis(2,4,6-tribromophenoxy)-2,3-dibromo-2-          butene     ______________________________________

The certain bis-phenoxy compounds (BPC) listed in the Tables under Present Invention, as II, III, VI, etc. correspond to those compounds listed on pages 11 and 12 of this specification.

The control (base resin) is the particular designated polymer without the PAC, BPC or EA.

The results of this comparative testing are set forth in Tables IV through XVII.

                                      Table IV     __________________________________________________________________________                Con-                trol                    Prior Art               Present Invention     Resin ABS  (Base                    Compounds               Compounds     Additive 15/5                Resin                    A   B   C   D   E   F   II  III IV  IV  VIII                                                                IX     __________________________________________________________________________     Oxygen Index, %     at 73° F                18.5                    21.5                        28.0                            27.5                                35.0                                    26.0                                        34.5                                            30.5                                                28.0                                                    30.5                                                        31.0                                                            36.0                                                                30.0     UL-94 1/8" thickness                HB  HB  V-0 V-0 V-0 HB  V-0 V-0 V-0 V-0 V-0 V-0 V-0     Xenon Arc     Weather-Ometer                5   6   12  10  13  3   11  7   8   9   2   1   4      (Ranked)     Injection Molded     Initial Color                White                    Off-                        Off-                            Off-                                Tan Off-                                        Light                                            White                                                White                                                    White                                                        White                                                            White                                                                White                    White                        White                            White   White                                        Cream     Visual Migration       Initial      None                        None                            None                                None                                    None                                        None                                            None                                                None                                                    None       7 days       None                        None                            None                                None                                    None                                        None                                            None                                                None                                                    None     TGA 5% wt. loss ° C                    266     249     Isotherm 72 hr.,                329 48 hr.                        307 48 hr.                                261 271 274 285 290 310      150° C                1.83                    0.415   0.727       1.27                                            1.11     Melt Flow g/10 min.     Conditions "G"                3.2 3.6 4.0 4.5 8.3 9.9 4.9 8.2 6.7 3.4     200° C,5,000 g     Notched Izod Impact     ft. lbs/in. 1/2 × 1/8                3.27                    1.62                        1.40                            1.19                                1.56                                    1.62                                        1.23                                            1.93                                                2.12                                                    1.19                                                        2.08                                                            1.92                                                                1.32     Heat Deflection Temp.      ° F at 265 psi                192 189 187 190 184 171 185 180 176 190      Annealed at 180° F     Concentrate Compounding     Temperature, ° F                    400 400 400 400 400 400 450 350 400 400 400 400     Injection Molding     Temperature, ° F                450 450 450 450 450 450 430 450 450 450 450 450 450     Gardner Color     Value, Δ E     After 100 hours,                6.5 3.9 20.1                            11.9                                12.7                                    4.6 8.6 6.7 7.9 7.3 0.9 4.1 1.1     Xenon Arc     __________________________________________________________________________

                                      Table V     __________________________________________________________________________                   Control                        Prior Art               Present Invention     Resin ABS     (Base                        Compounds               Compounds     Additive 20/0 Resin                        A   B   C   D   E   F   II  III IV                                                          VI  VIII                                                                 IX     __________________________________________________________________________     Oxygen Index, %     at 73° F                   18.5 20.5                            24.5                                24.0                                    27.0                                        22.5    24.0                                                    22.5  27.0     UL-94 1/8" thickness                   HB   HB  HB  V-0 V-0 HB      HB  HB    V-0     Xenon Arc     Weather-Ometer (Ranked)                   1    5   7   6   8   1       2   3     4     Injection Molded                   White                        Off-                            Off-                                Off-                                    Tan White                                            De- White                                                    White off-     Initial Color      White                            White                                White       com-          White                                            posed     Visual Migration     Initial            None                            None                                None                                    None                                        None    None                                                    None  None     7 days     TGA 5% wt. loss ° C     Isotherm 72 hr., 150° C     Melt Flow g/10 min.     Conditions "G" 200° C,5,000g     Notched Izod Impact     ft.lbs/in. 1/2  × 1/8                   3.27 1.40                            1.43                                1.17                                    1.15                                        1.97    3.27                                                    4.18  1.45     Heat Deflection Temp.     ° F at 264 psi,     Annealed at 180° F     Concentrate Compounding     Temperature, ° F                        400 400 400 400 400 400 400 400   400     Injection Molding     Temperature, ° F                   450  450 450 450 420 450     450 450   450     Gardner Color Value, Δ E     After 100 hours, Xenon Arc                   6.5  8.0 19.8                                11.1                                    8.5 4.6     4.4 5.2   5.6     __________________________________________________________________________

                                      Table VI     __________________________________________________________________________                   Control                         Prior Art              Present Invention     Resin ABS     (Base                        Compounds               Compounds     Additive 30/0 Resin)                        A   B   C   D   E   F   II  III IV VI  VIII                                                                  IX     __________________________________________________________________________     Oxygen Index, %                   18.5 21.5                            30.0                                30.0                                    32.0                                        27.0                                            30.0                                                33.5                                                    34.0   35.5     at 73° F     UL-94 1/8" thickness                   HB   HB  V-0 V-0 V-0 V-0 V-0 V-0 V-0    V-0     Xenon Arc     Weather-Ometer (Ranked)                   3    5   10  8   11  1   7   4   2      6     Injection Molded   Egg Egg Egg                        Egg     Initial Color White                        Shell                            Shell                                Shell                                    Light                                        White                                            Light                                                White                                                    White  Shell                        White                            White                                White                                    Brown   Tan            White     Visual Migration      Initial      7 days     TGA 5% wt. loss ° C     Isotherm 72 hr., 150° C     Melt Flow g/10 min.     Conditions "G" 200° C,5,000g     Notched Izod Impact     ft. lbs/in. 1/2 × 1/8                   3.27 1.06                            1.08                                1.09                                    1.50                                        1.42                                            1.19                                                2.49                                                    3.65   1.13     Heat Deflection Temp.     ° F at 264 psi,     Annealed at 180° F     Concentrate Compounding                    --  440 440 440 392 392 356 440 400    440     Temperature, ° F     Injection Molding     Temperature, ° F                   450  450 450 450 400 430 400 450 450    450     Gardner Color Value, Δ E     After 100 hours, Xenon Arc                   6.5  1.4 9.0 2.6 6.5 1.6 2.5 2.6 1.2    0.8     __________________________________________________________________________

                                      Table VII     __________________________________________________________________________                 Control                      Prior Art               Present Invention     Resin HIPS  (Base                      Compounds               Compounds     Additive 12/4                 Resin)                      A   B   C   D   E   F   II  III IV                                                        VI  VIII                                                                IX     __________________________________________________________________________     Oxygen Index %     at 73° F                 18.5 20.0                          26.0                              23.5                                  27.0                                      23.0                                          25.0                                              21.0                                                  23.0  25.5                                                            26.5                                                                26.0     UL-94 1/8" thickness                 HB   HB  V-0 V-0 V-0 HB  V-2 HB  HB    V-0 V-0 HB     Xenon Arc     Weather-Ometer (Ranked)                 1    5   11  10  12  3   9   4   6     8   2   7     Injection Molded                 White                      Light                          Cream                              Grey                                  Light                                      White                                          Tan Off-                                                  Off-  Off-                                                            Off-                                                                Off-     Initial Color    Cream   Cream                                  Cream       White                                                  White White                                                            White                                                                White     Visual Migration     Per-                              Per-    Per-                          haps                              haps    haps     Initial     None None                          Slight                              Slight                                  None                                      Slight                                          None                                              None                                                  None  None     7 days      None None                          None                              None                                  None                                      None                                          None                                              None                                                  None  None     TGA 5% wt. loss ° C                 322  270 325 263 254 279 277 304 305   325     Isotherm    48 hr., 150° C                      0.582                 0.410                      1.44                          0.301                              1.04                                  3.12                                      1.17                                          0.885                                              0.940                                                  0.758 0.22     Melt Flow g/10 min.     Conditions "G" 200° C,     5,000g      6.2  11.0                          8.8 10.4                                  13.3                                      11.1                                          15.8                                              10.7                                                  13.8  7.1     Notched Izod Impact     ft.lbs/in. 1/2 × 1/8                 2.12 1.61                          1.71                              1.66                                  1.65                                      1.64                                          1.25                                              1.76                                                  1.63  1.69                                                            1.73                                                                1.72     Heat Deflection Temp.     ° F at 264 psi,     Annealed at 180° F                 182  171 180 171 165 157 172 172 157   177     Concentrate     Compounding     Temperature, ° F                 --   400 400 400 400 400 400 450 400   400 400 400     Injection Molding     Temperature, ° F                 450  450 450 450 450 430 430 450 430   450 450 450     Gardner Color Value,     ΔE     After 24 hours,     Xenon Arc   0.7  17.6                          3.6 13.9                                  34.3                                      7.0 11.0                                              11.0                                                  20.9  14.4                                                            4.3 16.3     __________________________________________________________________________

                                      Table VIII     __________________________________________________________________________               Control                    Prior Art                 Present Invention     Resin HIPS               Base Compounds                 Compounds     Additive 16/0               Resin)                    A   B   C   D    E   F         III  IV                                                          VI   VIII                                                                  IX     __________________________________________________________________________     Oxygen Index, %     at 73° F               18.5 18.5                        22.0                            22.0     21.5     21.0 21.5   22.0     UL-94     1/8"thickness               HB   HB  V-2 HB       HB       HB   HB     HB     Xenon Arc     Weather-Ometer     (Ranked)  1    2   9   7        5        3    6    4     Injection Molded               White                    Off-                        Cream                            Cream                                Decom-                                     White                                         Decom-                                              Off- White  Cream     Initial Color  White       posi-    posi-                                              White                                tion     tion     Visual Migration       Initial      None                        None                            None     None     None None   None       7 days       None                        None                            None     None     None None   None     TGA 5% wt.     loss ° C Isotherm     72 hr. 150° C     Melt Flow g/10     min. Conditions     "G" 200 C 5000g     Notched Izod     Impact ft.lbs/in.     12 × 1/8               2.12 1.64                        1.69                            1.58     1.59     1.62 1.60 1.66     Heat Deflection     Temp. ° F at 264 psi,     Annealed at 180° F     Concentrate     Compounding     Temperature, ° F                    400 400 400      400      400  400    400     Injection Molding               450  450 450 450      450      450  450    450     Gardner Color     Value, ΔE     After 24 hours,     Xenon Arc 0.7  19.4                        25.9                            23.2     21.7     34.0 30.5   17.8     __________________________________________________________________________

                                      Table IX     __________________________________________________________________________                     Control                          Prior Art              Present Invention     Resin HIPS      (BASE                          Compounds              Compounds     Additive 30/0   Resin)                          A   B   C   D   E   F  II  III IV                                                           VI  VIII                                                                  IX     __________________________________________________________________________     Oxygen Index, %     at 73° F 18.5 21.0                              25.5                                  26.5                                      30.0                                          25.0                                              27.0                                                 27.0                                                     25.0  32.0     UL-94 1/8" thickness                     HB   HB  V-0 V-0 V-0 V-0 V-0                                                 V-0 V-0   V-0     Xenon Arc     Weather-Ometer (Ranked)                     1    5   10  7   9   2   8  4   6     3     Injection Molded                     Trans-                          Biege                              Light                                  Grey                                      Brown                                          Light                                              Tan                                                 Off-                                                     Off-  Light     Initial Color   luscent  Grey        Tan    White                                                     White Biege     Visual Migration     Initial     7 days     TGA 5% wt. loss ° C     Isotherm 72 hr., 150° C     Melt Flow g/10 min.     Conditions "G" 200° C,5,000g     Notched Izod Impact     ft.lbs/in. 1/2 × 1/8                     2.12 1.10                              1.21                                  1.43                                      1.45                                          1.27                                              1.11                                                 1.39                                                     1.35  R 1.08                                                            1.10     Heat Deflection Temp.     ° F at 264 psi,     Annealed at 180° F     Concentrate Compounding     Temperature, ° F                          450 450 430 356 392 356                                                 450 400   450     Injection Molding     Temperature, ° F                     450  430 430 410 380 400 380                                                 430 410   430     Gardner Color Value, ΔE     After 24 hous, Xenon Arc                     0.7  22.4                              29.7                                  15.8                                      10.4                                          5.1 12.1                                                 17.2                                                     24.9  6.8     __________________________________________________________________________

                                      Table X     __________________________________________________________________________                   Control                       Prior Art                Present Invention     Resin Polycarbonate                   (Base                       Compounds                Compounds     Additive 3/1  Resin)                       A    B   C   D   E   F   II   III  IV                                                           VI  VIII                                                                  IX     __________________________________________________________________________     Oxygen Index, %     at 73° F                   25.0                       36.5 41.5                                39.5                                    39.5                                        37.0    36.5 37.5  40.0     UL-94 1/8" thickness                   HB  V-2  V-0 V-2 V-2 V-0     V-0  V-0   V-0     Xenon Arc     Weather-Ometer (Ranked)                   1   5    10  8   9   3       2    4     7     Injection Molded                   Clear                       Light                            Light                                Light                                    Cream                                        Light                                            De- Off- Cream Off-     Initial Color     Cream                            Cream                                Cream   Cream                                            com-                                                White      White     Visual Migration  Perhaps              po- Perhaps     Initial           Slight                            None                                None                                    None                                        None                                            si- Slight                                                     None  None     7 days            None None                                None                                    None                                        None                                            tion                                                None None  None     TGA 5% wt. loss ° C                   427 381  379 375 366 378     398  374   388     Isotherm 24 hr. 200° C                   0.394                       1.20 0.529                                1.78                                    1.18                                        1.12    0.664                                                     0.655 0.326     Melt Flow g/10 minl     Conditions "G" 275° C,1,200g                   9.8 11.8 12.7                                18.8                                    17.2                                        16.8    8.8  17.4  11.4     Notched Izod Impact     ft. lbs/in. 1/2 × 1/8                   16.50                       6.64 8.54                                2.73                                    1.02                                        3.16    16.98                                                     7.25  9.4     Heat Deflection Temp.     ° F at 264 psi,                   279 265  267 260 259 262     265  259   268     Annealed at 180° F              De-     Concentrate Compounding                grad-     Temperature, ° F                       500  480 480 500 500 ed at                                                500  500   500                                            500     Injection Molding     Temperature, ° F                   520 520  520 520 520 520     520  520   520     Gardner Color Value, ΔE     After 48 hours, Xenon Arc                   1.1 4.7  22.2                                10.1                                    6.7 3.8     3.6  3.6   9.6     __________________________________________________________________________

                                      Table XI     __________________________________________________________________________                    Control                         Prior Art               Present Invention     Resin Nylon 6  (Base                         Compounds               Compounds     Additive 12/4  Resin)                         A   B   C   D   E   F   II  III IV                                                           VI  VIII                                                                  IX     __________________________________________________________________________     Oxygen Index, %     at 73° F                    21.5 26.0                             28.5                                 29.0            24.5      27.5                                                     Mold-     UL-94 1/8" thickness                    HB   V-2 V-0 V-2 Did De- Did V-2 ing   V-0     Xenon Arc                       Not com-                                             Not     Prob-     Weather-Ometer (Ranked)         Mold                                         posed                                             Mold    lems     Injection Molded                    Natural                      Off-                                                     De-     Initial Color  (white)                         Cream                             Cream                                 Cream           White                                                     com-  Cream                                                     posed     Visual Migration     Initial             None                             None                                 None            None      None     7 days              None                             None                                 None            None      None     TGA 5% wt. loss ° C                    237  219 219 204             214       220     Isotherm 48 hr. 150° C                    5.67 4.70                             4.60                                 4.76            4.49      4.97     Melt Flow g/10 min.     Conditions "G" 10° C 5000g     Notched Izod Impact     ft.lbs/in. 1/2 × 1/8                    3.09 1.85                             1.66                                 1.60            2.54      2.20     Heat Deflection Temp.     ° F at 264 psi,                    125  137 133 135             132       136     Annealed at 200° F     Concentrate Compounding     Temperature, ° F                         440 440 440     440     440       440     Injection Molding     Temperature, ° F                    480  480 480 480     450     480       480     Gardner Color Value, ΔE     After 100 hours, Xenon Arc                    0.9  2.0 3.7 2.5             2.4       7.9     __________________________________________________________________________

                                      Table XII     __________________________________________________________________________                Con-                trol                    Prior Art                  Present Invention     Resin Polypropylene                (Base                    Compounds                  Compounds     Additive 12/4                Resin)                    A    B    C   D   E    F   II   III  IV                                                           VI  VIII                                                                  IX     __________________________________________________________________________     Oxygen Index, %     at 73° F                17.5                    21.0 24.0 25.0                                  24.0                                      20.5 31.5                                               21.5 23.5   23.0     UL-94 1/8" thickness                HB  HB   V-2  HB  V-2 HB   V-0 HB   V-2    HB     Xenon Arc     Weather-Ometer     (Ranked)   1   4    11   9   10  5    8   3    2      6     Injection Molded                Clear                    Off- Off- Cream                                  Cream                                      Off- Cream                                               Off- Off-. Off-     Initial Color  White                         White        White    White                                                    White  White     Visual Migration                    Perhaps           Perhaps  Perhaps                                                    Perhaps     Initial        Slight                         Perhaps                              None                                  None                                      Slight   Slight                                                    Slight None     7 days         Perhaps                         Slight                              None                                  None                                      None     Perhaps                                                    Perhaps                                                           None                    Slight                         None                  Slight                                                    Slight     TGA 5%     wt. loss ° C                272 264  274  256 252 260  269 275  273    276     Isotherm 48 hr.                0.00     150° C                0.20                    0.937                         0.493                              3.7 13.6                                      2.14 0.756                                               0.607                                                    0.873  0.33     Melt Flow     g/10 min.     Conditions "L",     230° C, 2,160g                5.2 9.3  6.8  9.8 9.3 9.9  17.7                                               10.4 8.9    6.4     Notched     Izod Impact     ft.lbs/in. 1/2 × 1/8                1.22                    1.19 1.21 1.12                                  1.16                                      1.13 1.10                                               0.96 1.07   1.20     Heat     Deflection Temp.     ° F at 66 psi,     Annealed at 194° F                246 253  240  276 240 235  267 267  257    277     Concentrate     Compounding     Temperature, ° F                    400  420  400 360 450  420 400  400    400     Injection Molding     Temperature, ° F                440 440  440  440 440 440  400 440  440    440     Gardner Color     Value, ΔE     After 48 hours,     Xenon Arc  0.5 5.3  12.8 10.0                                  8.8 5.7  7.3 2.7  2.7    4.8     __________________________________________________________________________

                                      Table XIII     __________________________________________________________________________                    Control                         Prior Art               Present Invention     Resin Polyester                    (Base                         Compounds               Compounds     Additive 12/4  Resin)                         A   B   C   D   E   F   II  III IV                                                           VI  VIII                                                                  IX     __________________________________________________________________________     Oxygen Index, %     at 73° F                    22.0 28.0                             32.0                                 32.0                                     32.0                                         26.0    30.0                                                     29.0  32.0     UL-94 1/8" thickness                    HB   V-2 V-0 V-0 V-0 V-2     V-2 V-2   V-0     Xenon Arc     Weather-Ometer (Ranked)                    1    5   9   7   8           3   2     4     Injection Molded                    White                         Off-                             Off-                                 Off-                                     Cream                                         Cream                                             De- White                                                     White Cream     Initial Color       White                             White                                 White       com-     Visual Migration     Initial             None                             None                                 None                                     None                                         None                                             posi-                                                 None                                                     None  None     7 days              None                             None                                 None                                     None                                         None                                             tion                                                 None                                                     None  None     TGA 5% wt. loss ° C                    369  281 346 266 292 305     311 330   351     Isotherm 24 hr. 200° C                    0.576                         1.97                             0.115                                 3.66                                     4.67                                         2.89    1.99                                                     0.606 0.446                    0.489     Melt Flow g/10 min.                    15.0 11.5                             12.8                                 10.8                                     22.0                                         16.5    6.5 25.8  11.3     Conditions "H", 230° C,1,260g     Notched Izod Impact                    1.51 1.04                             1.00                                 1.07                                     0.96                                         1.12    1.19                                                     1.33  0.90     ft.lbs/in. 1/2 × 1/8     Heat Deflection Temp.     ° F at 264 psi                    123  122 127 127 121 123 117 122 139     Annealed at 100° F     Concentrate Compounding     Temperature, ° F                         450 450 450 450 450     450 450   450     Injection Molding     Temperature, ° F                    470  460 460 460 470 470     460 470   460     Gardner Color Value, Δ E     After 24 hours, Xenon Arc                    1.9  7.8 22.6                                 7.3 8.5 1.9     3.4 3.1   4.2     __________________________________________________________________________

                                      Table XIV     __________________________________________________________________________                    Control                         Prior Art         Present Invention     Resin Polyester                    (Base                         Compounds         Compounds     Additive 16/0  Resin)                         A   B   C   D E F II  III IV                                                     VI  VIII                                                            IX     __________________________________________________________________________     Oxygen Index, %     at 73° F                    22.0 28.0                             23.0                                 28.5      27.5                                               27.5  27.5     UL-94 1/8" thickness                    HB   V-2 V-2 V-2       V-22                                               V-2   V-2     Xenon Arc     Weather-Ometer (Ranked)     Injection Molded     Initial Color  White                         Off-                             Light                                 Light     Off-                                               White White                         White                             Tan Grey      White     Visual Migration     Initial     7 days     TGA 5% wt. loss ° C     Isotherm 24 hr., 200° C     Melt Flow g/10 min.     Conditions "H", 230° C,1,260g     Notched Izod Impact                    1.51 0.93                             1.32                                 1.13      1.19                                               1.33  1.13     ft. lbs/in. 1/2 × 1/8     Heat Deflection Temp.     ° F at 264 psi,     Annealed at 100° F     Concentrate Compounding                         450 450 450       470 470   450     Temperature, ° F     Injection Molding                    470  460 460 460       460 460   460     Temperature, ° F     Gardner Color Value, Δ E     After 24 hours, Xenon Arc     __________________________________________________________________________

                                      Table XV     __________________________________________________________________________                    Control                         Prior Art                Present Invention     Resin PPO      (Base                         Compounds                Compounds     Additive 9/3   Resin)                         A   B   C   D   E    F   II  III IV                                                            VI VIII                                                                  IX     __________________________________________________________________________     Oxygen Index, %     at 73° F                    26.5 25.0                             30.0                                 28.0                                     31.0                                         27.0 30.0                                                  27.5                                                      29.0  27.0     UL-94 1/8" thickness                    V-1  V-1 V-0 V-0 V-0 V-0  V-0 V-0 V-0   V-0     Xenon Arc     Weather-Ometer (Ranked)     Injection Molded                    Brown                         Brown                             Brown                                 Brown                                     Brown                                         Brown                                              Brown                                                  Brown                                                      Brown Brown     Initial Color     Visual Migration                    Perhaps     Initial             None                             None                                 None                                     None                                         Slight                                              None                                                  None                                                      None  None     7 days              None                             None                                 None                                     None                                         None None                                                  None                                                      None  None     TGA 5% wt. loss ° C                    281  249 294 244 243 262  261 277 276   279     Isotherm 24 hr. 200° C                    1.87 4.07                             2.21                                 5.00                                     3.88                                         3.19 5.40                                                  3.08                                                      3.19  2.35     Melt Flow g/10 min.                    1.4  3.3 2.1 2.6     3.7      3.8 3.0   1.9     Conditions     Notched Izod Impact                    4.02 2.39                             2.44                                 2.44                                     1.94                                         2.97 1.77                                                  2.50                                                      2.60  1.89     ft.lbs/in. 1/2 × 1/8     Heat Deflection Temp.     ° F at 264 psi,                    209  196 205 200 200 177  194 193 190   203     Annealed at 200° F     Concentrate Compounding                         450 450 450 450 450  450 450 450   450     Temperature, ° F     Injection Molding                    450  450 450 450 450 450  450 450 450   450     Temperature, ° F     Gardner Color Value, Δ E     After hours, Xenon Arc     __________________________________________________________________________

                                      Table XVI     __________________________________________________________________________                    control                         Prior Art              Present Invention     Resin PPO      (Base                         Compounds              Compounds     Additive 9/3 (Pigmented)                    Resin)                         A  B   C   D   E   F   II  III IV VI  VIII                                                                  IX     __________________________________________________________________________     Oxygen Index, %     at 73° F                    25.0    32.0                                31.0                                    33.5                                        26.5                                            32.5                                                28.0                                                    28.5   30.0     UL-94 1/8" thickness                    HB      V-0 V-0 V-0 V-0 V-0 V-0 V-0    V-0     Xenon Arc     Weather-Ometer (Ranked)                    1       9   6   8   1   7   3   2      4     Injection Molded                    Light   Light                                Light   Light                                            Dark                                                Light                                                    Light  Light     Initial Color  Tan     Tan Tan Tan Tan Tan Tan Tan     Visual Migration                    None    None                                None                                    None                                        None                                            None                                                None                                                    None   None     7 days         None    None                                None                                    None                                        None                                            None                                                None                                                    None   None     TGA 5% wt. loss ° C                    389     335 284 291 311 275 338 324    337     Isotherm 24 hr. 200° C                    0.299   0.420                                0.893                                    0.865                                        0.587                                            1.02                                                0.556                                                    0.272  0.476     Melt Flow g/10 minl     Conditions     Notched Izod Impact                    3.24    2.14                                2.00                                    1.19                                        2.02                                            1.40                                                2.16                                                    2.18   1.82     Heat Deflection Temp.     ° F at 264 psi,                    246     233 226 227 210 221 210 207    237     Annealed at 200° F     Concentrate Compounding                    450     450 450 450 450 450 450 450    450     Temperature, ° F     Injection Molding                    460     460 460 460 460 460 460 460    460     Temperature, ° F     Gardner Color Value, Δ E                    3.6     13.3                                9.2 9.0 5.9 14.8                                                5.3 4.9    6.9     After 48 hours, Xenon Arc     __________________________________________________________________________

                                      Table XVII     __________________________________________________________________________                    Control                         Prior Art              Present Invention     Resin LDPE     (Base                         Compounds              Compounds     Additive 20/5  Resin)                         A B    C   D   E   F   II  III IV                                                          VI  VIII                                                                 IX     __________________________________________________________________________     Oxygen Index, %     at 73° F                    18.0   28.0 29.0                                    27.0                                        26.5                                            26.5                                                26.0                                                    28.0  26.5   25.5     UL-94 1/8" thickness                    HB     V-0  V-2 V-2 V-2 V-2 V-2 V-0   V-0    V-2     Xenon Arc     Weather-Ometer (Ranked)     Injection Molded                    Natural                           Off- Light                                    Off-                                        White                                            Cream                                                White                                                    White White     Visual Migration     Initial               None Yes Yes None                                            None                                                None                                                    Yes   None     7 days                None Yes Yes None                                            Yes None                                                    Yes   None     TGA 5% wt. loss ° C                    302    330  248 248 265 267 305 308   332     Isotherm 48 hr. 150° C                    0      0    1.84                                    2.42                                        0.78                                            0.66                                                0.26                                                    0.41  0.16     Melt Flow g/10 min.     Conditions "G" 200 C 5000g     Notched Izod Impact                    NB     NB   NB      NB  NB      NB    NB     NB     ft. - lbs/in. 1/2 × 1/8                    >6.6   >7.1 >7.9                                    3.31                                        >7.3                                            >8.3                                                2.12                                                    >8.8  >8.1     Heat Deflection Temp.     ° F at 264 psi     Annealed at 180° F     Concentrate Compounding     Temperature, ° F                    400    400  400 400 400 400 450 400   400    400     Temperature, ° F     Injection Molding     Temperature, ° F                    430    450-410                                410 410 410 410 410 430   410     Gardner Color Value, Δ E     After 100 hours, Xenon Arc                    0.4    9.8  8.5 4.4 2.1 7.5 3.9 1.3   3.0    2.4     __________________________________________________________________________

Referring to Tables IV through XVII in general, it is readily apparent that the incorporation of additives in polymer systems is highly unpredictable. Even in the same polymer, "structurally related " prior art compounds and the bis-phenoxy compounds (of the present invention) produced completely different results. For example, Table IV shows the results of testing an ABS polymer containing 15% PAC or BPC and 5% EA. The ABS/BPC/EA combination is the only one which produced V-O (UL 94), white color Δ E values substantially the same as the control (without additives) and superior thermal stability. While B, C, D, and F (prior art compounds) yielded a V-O (UL 94) composition, the Δ E values were excessively high and thus non-applicable for commercial ABS uses. A and E show non-efficacy (HB ratings like the control) thereof as flame retardants and again point out the non-predictability of additives incorporated in either the same or various polymers. (The inclusion of data, relating to where no enhancing agent is used, is present to show non-efficacy of BPC at low concentrations and the large quantities required to produce efficacy--note Tables V and VI.) In conjunction with the present invention polymer system (BPO), Tables XV and XVI are illustrative thereof. For example, while B, C, D, and F produced V-O (UL 94), the Gardner Color Values, Δ E, were substantially high and thus non-appplicable for commercial PPO uses. Thus, out of all the data shown herein, (Examples I through VIII), it is clear that the combination of the bis-phenoxy compounds and enhancing agent result in an unexpected, superior, flame retarded PPO composition which has commercial application as compared to most other polymers.

EXAMPLE IX

The procedure of Examples I and II are repeated except that the bis-phenoxy compound used corresponds to Formula V heretofor set forth, insteand of Formula II and III. Substantially the same results are obtained using the Formula V compound as those obtained using the Formulae II and III compounds.

EXAMPLE X

The procedure of Examples IX, VII, VIII are repeated except that the enhancing agent used in zinc borate instead of antimony oxide. Substantially the same results are obtained using zinc borate as those using antimony oxide.

EXAMPLE XI

The bis-phenoxy compounds described herein are subjected to toxicity tests and it is found that these compounds are not toxic orally, not irritating to the eye and not irritating to the skin, all as measured by the guidelines of the Federal Hazardous Substances Act. Furthermore, rat feeding studies indicate these materials are not biologically persistent, an important property to minimize ecological imbalance.

In summary, the results shown in Tables IV through XVII (in addition to those set forth in Example I) are reviewed with the aforementioned criteria, i.e. UL 94 rating V-O and physical properties such as thermal stability, and are presented in Table XVIII in terms of whether there is commercial utility, (taking into consideration all physical and mechanial properties), i.e. similar to those results shown for octabromobiphenyl in Modern Plastics Encyclopedia, ibid. Table XVIII sets forth more vividly the different between the present invention and the prior art and also the different results obtained when different polymers have the same additives incorporated therein; and also confirming those specific observations regarding the difference in polymer systems as noted by the Norris et. al paper, ibid.

                                      TABLE XVIII     __________________________________________________________________________     FLAME RETARDANT EFFICACY OF DIFFERENT ADDITIVES IN DIFFERENT POLYMER     SYSTEMS     (IS THERE COMMERCIAL UTILITY BASED ON A PPO POLYMER SYSTEM CRITERIA?)                    Prior Art         Present Invention     Polymers       Compounds + Enhancing Agents                                      Compounds + Enhancing Agents     __________________________________________________________________________     I. Present Invention                    A  B  C  D  E  F  II III                                            VI IV VIII                                                     IX X     Polyphenylene oxide (PPO)                       Yes                          Yes                             Yes                                Yes                                   Yes                                      Yes                                         Yes                                            Yes     II. Comparative Polymers     Polystyrene (HIPS)                    No.                       ?* ?* ?* No No No No Yes      No Yes     Polycarbonate  No ?* No No Yes                                   No Yes                                         Yes                                            Yes     Nylon          No yes                          No    No    No No Yes     Polypropylene  No No No No No Yes                                      No No No     Polyester      No No Yes                             Yes                                Yes                                   No No No Yes     Poylsulfone                      Yes                                         Yes                                            Yes                                               Yes     Polyethylene (LDPE)                       ?* No No No No No Yes                                            Yes      No     Polyacrylonitrile                No No     Polymethylmethacrylate           No No     ABS            No ?* ?* ?* No Yes                                      Yes                                         Yes                                            Yes                                               Yes                                                  Yes                                                     Yes     __________________________________________________________________________      (*Perhaps Δ E values very high)

In view of the foregoing Examples and remarks, it is seen that the plastic compositions, which incorporate a three component system (including the bis-phenoxy compounds), possess characteristics which have been unobtainable in the prior art. Specifically, the use of bis-phenoxy compounds and enhancing agents in a PPO polymer as flame retardants therefor is quite unique since it is not possible to predict the effectiveness and functionality of any particular material in any polymer system until it is actively undergone incorporation therein and the resultant plastic composition evaluated according to certain criteria such as UL-94 and various ASTM Standards. Furthermore, it is necessary, in order to have commercial utility, that the resultant flame retarded plastic composition possess characteristics such as being non-toxic and not biologically persistent. Use of the bis-phenoxy compounds and an enhancing agent in a PPO polymer has accomplished all of these objectives.

Thus, in order to meet the needs and standards of commerce, it is necessary that a successful candidate fulfill all of the requirements outlined above, not just a selected group. It was totally unexpected that this specific group of bis-phenoxy compounds meet these requirements in all aspects contrary to the expectations of the suggested teachings of the prior art.

The above examples have been described in the foregoing specification for the purpose of illustration and not limitation. Many other modifications and ramifications will naturally suggest themselves to those skilled in the art based on this disclosure. These are intended to be comprehended as within the scope of this invention. 

What is claimed is
 1. A plastic composition comprising a three component system consisting of (1) a poly(phenylene oxide), (2) a bisphenoxy compound, which functions as a flame retardant for said composition, having the formula ##STR7## wherein (a) Z is bromine; (b) m abd m' are independent and are integers having a value of from 1 to 5 with the proviso that the bromine atom content is from 6 to 10 bromine atoms; and (c) T is a straight or branched chain carbon group having from one to four carbon atoms, and (3) a flame retardant enhancing agent.
 2. The composition as set forth in claim 1 wherein the amount of said bis-phenoxy compound employed is from about 1% to about 25% by weight, based on the total weight of said composition.
 3. The composition as set forth in claim 2 wherein the T is CH₂.
 4. The composition as set forth in claim 2 wherein the T is (CH₂)₂.
 5. The composition as set forth in claim 2 wherein the T is (CH₂)₃.
 6. The composition as set forth in claim 2 wherein the T is (CH₂)₄.
 7. The composition as set forth in claim 2 wherein the T is ##STR8##
 8. The composition as set forth in claim 2 wherein the T is ##STR9##
 9. The composition as set forth in claim 2 wherein the enhancing agent is selected from the group consisting of oxides and halides of Groups IV A and V A of the Periodic Table of Elements.
 10. The composition as set forth in claim 9 wherein the T is (CH₂)₂ and m and m' are each
 5. 11. The composition as set forth in claim 9 wherein the T is (CH₂)₂ and m and m' are each
 3. 12. The composition as set forth in claim 9 wherein the T is (CH₂)₃ and m and m' are each
 3. 13. The composition as set forth in claim 9 wherein the T is (CH₂)₄ and m and m' are each
 3. 14. The composition as set forth in claim 9 wherein the T is CH₂ and m and m' are each
 3. 15. The composition as set forth in claim wherein the T is CH₂ and m' are each
 5. 16. The composition as set forth in claim 9 wherein the T is (CH₂)₂ and m is 5 and m' is
 3. 17. The composition as set forth in claim 9 wherein the enhancing agent is antimony oxide.
 18. A flame retarded, shaped compositions comprising a three component system which consists of (a) a poly (phenylene oxide), (b) a bis-phenoxy compound selected from the group consisting of (i), 1,2-bis (2,4,6-tribromophenoxy) ethane, (II) 1,3,-bis(2,4,6-tribromophenoxy)propane and (iii) 1,2-bis(2,3,4,5,6-pentabromophenoxy)ethane and (c) an enhancing agent selected from the group consisting of oxides of antimony, arsenic and bismuth; with the provisio that said plastic composition is further characterized by having a flammability rating of SE-O (V-O) as determined by the UL 94 procedure described in the specification.
 19. The composition as set forth in claim 18 wherein (a) the bis-phenoxy compound is 1,2-bis(2,4,6-tribromophenoxy)ethane and is present in an amounnt of from about 1% by weight to about 20% by weight, based on the total weight of said composition and (b) the enhancing agent is antimony trioxide and is present in an amount of from about 0.5% by weight to about 10% by weight, based on the total weight of said composition.
 20. A composition as set forth in claim 19 wherein the amount of said bis-phenoxy compound is about 5% by weight, based on the total weight of said composition, said enhancing agent is present in an amount of about 3% by weight, based on the total weight of said composition, the tensile strength is about 11,500 psi and the Notched Izod Impact is about 0.9 ft. lbs./in.
 21. A composition as set forth in claim 19 wherein the amount of said bis-phenoxy compound is about 10% by weight, based on the total weight of said composition, and said enhancing agent is present in an amount of about 3% by weight, based on the total weight of said composition.
 22. The composition as set forth in claim 18 wherein (a) the bis-phenoxy compound is 1,3-bis(2,4,6-tribromophenoxy)propane and is present in an amount of from about 1% by weight to about 20% by weight, based on the total weight of said composition and (b) the enhancing agent is antimony trioxide and is present in an amount of from about 0.5% by weight to about 10% by weight, based on the total weight of said composition.
 23. A composition as set forth in claim 22 wherein the amount of said bis-phenoxy compound is about 10% by weight, based on the total weight of said composition, said enhancing agent is present in an amount of about 3% by weight, based on the total weight of said composition, the tensile strength is about 11,800 psi and the Notched Izod Impact is about 1.0 ft.lbs./in.
 24. A composition as set forth in claim 22 wherein the amount of said bis-phenoxy compound is about 13% by weight, based on the total weight of said composition, and said enhancing agent is present in an amount of about 3% by weight, based on the total weight of said composition.
 25. A composition as set forth in claim 18 wherein (a) the bis-phenoxy compound is 1,2-bis(2,3,4,5,6-pentabromophenoy)ethane and is present in an amount of from about 1% by weight to about 20% by weight, based on the total weight of said composition and (b) the enchancing agent is antimony trioxide and is present in an amount of from about 0.5% by weight to about 10% by weight, based on the total weight of said composition.
 26. A composition as set forth in claim 25 wherein the bis-phenoxy compound is present in an amount of about 10% by weight, based on the total weight of said composition and the enhancing agent is present in an amount of about 3% by weight based on the total weight of said composition. 